• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to an organic electronic device containing first and second anode and cathode type electrodes and at least one assembly comprising a multilayer stack disposed between said electrodes, said multilayer stack comprising an N-type layer, an electrically active layer and a layer. P type consisting of a mixture of poly (3,4-ethylenedioxythiophene): poly (styrene-sulfonate) characterized in that said stack contains an additional layer called "tie layer" composed of at least one metal oxide and which is interposed between and in contact with the active layer and the P-type layer. It also relates to the method for preparing such a device.
    公开号:FR3013897A1
    申请号:FR1361618
    申请日:2013-11-26
    公开日:2015-05-29
    发明作者:Matthieu Manceau；Solenn Berson
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of organic electronic devices such as organic solar cells (OPV) or organic photovoltaic cells, organic light-emitting diodes (OLEDs), and organic photodetectors (OPDs).
    [0002] These devices consist of a first and a second electrode respectively disposed above and below a multilayer stack comprising in particular a so-called "active" layer adjacent to a so-called "P-type" layer. More specifically, the invention aims to improve the adhesion between this active layer and this P type layer.
    [0003] Organic electronic devices, and in particular organic solar cells, can be distinguished in terms of standard or inverse structure according to the order of succession of the layers constituting them. In a so-called standard structure, these layers are deposited in the following order: - substrate; transparent conductive layer as first electrode and forming the anode; - P-type semiconductor layer called "hole transport layer" or P-type layer; - electrically active layer called "active layer"; - N-type semiconductor layer called "electron transport layer" and N-type layer; and conductive layer as a second electrode and forming the cathode. In a so-called reverse or NIP structure, the stack is inverted and the layers are deposited in the following sequence: a substrate 1; a transparent conductive layer as first electrode 2 and forming the cathode; an N-type semiconductor layer 3 called an "electron transport layer" or an N-type layer; an electrically active layer 4 called "active layer"; a P-type semiconductor layer 5 called a P-type layer or a "hole-transport layer"; a conducting layer as a second electrode 6 or an upper electrode forming the anode. This second structure, illustrated in FIG. 1, is that which, to date, makes it possible to achieve the most important lifetime for this type of device. Generally, the P-type semiconductor layers considered in these structures are formed essentially from a mixture of two polymers, poly (3,4-ethylenedioxythiophene) (PEDOT) and sodium polystyrene sulfonate (PSS), said PEDOT: PSS. As such, these layers have the property of being hydrophilic. Moreover, the electrically active layers, conventionally considered in these structures, consist of a mixture containing at least two semiconductor materials: an N-type material, an electron acceptor, and a P-type material, which is a donor. electrons (hole transporter). These active layers are therefore generally hydrophobic. There is therefore naturally an incompatibility between these two types of layers (P type layer and active layer), which must nevertheless be superimposed on one another to ensure the proper operation of the devices. This lack of affinity also has the consequence of making it difficult to perform their stacking. In addition, once the deposition of these layers on each other carried out, the adhesion between said active layers and P type remains low, so that they naturally tend to peel off. This low adhesion makes it less easy to handle the cells containing this type of stack during their encapsulation, and also during their use, in particular, when used in flexible or conformable modules. Several solutions have already been envisaged to solve the problem of incompatibility between the active layer and the P layer. A solution proposed in the case of reverse structures aims to achieve a surface treatment with ozone and ultra-violet layer active to make it hydrophilic. However, this type of treatment affects the integrity of the active layer and therefore leads to a decrease in the efficiency of the final device (Lloyd et al Solar Energy Materials and Solar Cells, 95, 2011, 1382-1388). Another solution is to dip the stack in a solution (process called "dip coating" in English). However, this method comprises on the one hand a risk of degradation of the stack and on the other hand, it does not allow to control the thickness of the P-type layer deposited on the active layer. This solution can also lead to a decrease in the electrical performance of the module. Consequently, there remains a need for a solution making it possible to improve the adhesion between the P-type layer and the active layer and to guarantee the preservation of this satisfactory level of adhesion when using the corresponding cells. . The present invention precisely aims to meet this need. Thus, the invention provides an effective mode of adhesion between an active layer and a P layer and moreover, having improved properties in terms of stability, performance and service life. The invention also aims to propose a method for preparing an organic electronic device, in which the stack of a layer P and an active layer is easy to implement.
    [0004] The main subject of the present invention is an organic electronic device containing first and second electrodes and at least one assembly comprising a multilayer stack disposed between said electrodes, said multilayer stack comprising an N-type layer, an electrically-active layer and a layer of the type P based on a mixture of poly (3,4-ethylenedioxythiophene): poly (styrene-sulfonate) (PEDOT: PSS) in which said stack contains an additional layer called "tie layer" composed of at least one oxide metal and which is interposed between and in contact with the active layer and the P-type layer. In said device, the layers forming the stack are placed in this order of superposition from the first electrode: the N-type layer, the electrically active layer, the tie layer composed of at least one metal oxide and the P-type layer based on a mixture of poly (3,4-ethylenedioxythi ophène): poly (styrenesulfonate). The invention is furthermore directed to a method for preparing a multilayer stack, in particular constituting an OPV (inverse) cell, comprising an electrically active layer superimposed on an N-type layer, said method comprising the formation of a layer said "tie layer" interposed between and in contact with the so-called active layer and the P-type layer, said "tie layer" being formed of at least one metal oxide, preferably in the form of nanoparticles. More specifically, the present invention also provides a method for preparing an organic electronic device of inverse structure comprising at least the following steps: (i) having a substrate coated on one of its faces with a multilayer stack comprising in the order of superposition from said substrate: a conductive layer as a first electrode and an N-type layer; (ii) forming an electrically active layer on the N-type layer; (iii) contacting said active layer with a medium containing particles, and preferably nanoparticles, of at least one metal oxide, and exposing the assembly to conditions conducive to the formation of a so-called hook layer ; (iv) forming, by wet process, in contact with the tie layer, a P type layer composed of a mixture of two polymers, poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene sulfonate) ) sodium (PSS) said PEDOT: PSS; and (v) depositing in contact with the P-layer a conductive layer as a second electrode. According to another of these objects, the present invention relates to a method for improving the adhesion between an electrically active layer and a P-type layer, in an organic electronic device, said method consisting in forming a layer composed of at least one oxide metal at the intersection of the two layers. As is apparent from the following, the presence of the so-called contact layer and interposed between the so-called "active" and "P-type" layers is advantageous for several reasons.
    [0005] Firstly, it significantly improves the level of adhesion between these two layers, and the assembly exhibits an increased mechanical strength compared to a stack devoid of this tie layer. The realization of this layer is easy to implement and satisfactory in terms of quality.
    [0006] Indeed, this bonding layer can be formed from a simple deposit of a dispersion of metal oxide nanoparticles on the surface of the active layer of the OPV devices. It is not necessary to carry out a surface treatment beforehand. Lastly, this tie layer proves to be conducive to the formation of a uniform and homogeneous deposit of the layer P on contact with it. Other advantages and characteristics will appear on reading the following description, figures and examples. DESCRIPTION OF THE FIGURES FIG. 1: Organic Photovoltaic Cell in "Reverse" Structure (NIP). This cell comprises from bottom to top the following layers: a substrate 1; a first electrode 2 (cathode); an N type semiconductor layer 3; an electrically active layer 4; a P-type semiconductor layer; a second electrode 6 (anode) or upper electrode. Figure 2: Organic photovoltaic cell incorporating the bonding layer in so-called "reverse" structure (PIN). This cell comprises from bottom to top the following layers: a substrate 1; A first electrode 2 (cathode); an N type semiconductor layer 3; an active layer 4; a tie layer 0; a P-type semiconductor layer; a second electrode 6 (anode) or upper electrode. Figures 3 to 5 show several types of PIN devices in "tandem" mode, that is to say comprising several stacks and incorporating at least one tie layer. Figure 3: This cell comprises from bottom to top the following layers: a substrate 1; a first electrode 2 (cathode); an N type semiconductor layer 3; an active layer 4; a tie layer 0; a P-type semiconductor layer; An N-type semiconductor layer 3; an active layer 4; a P type semiconductor layer; a second electrode 6 (anode) or upper electrode. Figure 4: This cell comprises from bottom to top the following layers: a substrate 1; a first electrode 2 (cathode); an N type semiconductor layer 3; an active layer 4; a P-type semiconductor layer; an N-type semiconductor layer 3; an active layer 4; a tie layer 0; a P-type semiconductor layer; a second electrode 6 (anode) or upper electrode.
    [0007] Figure 5: This cell comprises from bottom to top the following layers: a substrate 1; a first electrode 2 (cathode); an N type semiconductor layer 3; an active layer 4; a tie layer 0; a P-type semiconductor layer; an N type semiconductor layer 3; an active layer 4; a tie layer 0; a P-type semiconductor layer; a second electrode 6 (anode) or upper electrode. DETAILED DESCRIPTION Bonding layer As is apparent from the above, the device considered according to the invention is characterized by the presence of a bonding layer, in the multilayer stack between its first and second electrodes. This attachment layer, considered in a device according to the invention, is in contact with, and interposed between the active layer and the P-type layer.
    [0008] The device has a reverse structure architecture and, more particularly, it is an organic photovoltaic cell in reverse structure. Thus, the bonding layer is formed in contact with the active layer, then the P-type layer is formed in contact with this bonding layer. The bonding layer used according to the present invention is a layer of metal oxide (s) in the form of nanoparticles. The nanoparticles are in particular particles having a maximum dimension of less than or equal to 200 nm. In the rest of the text, the expression "particle size" is used to characterize this maximum dimension.
    [0009] The metal oxide may be a P-type semiconductor metal oxide. In this case, the particles have a size between 2 nm and 200 nm. The metal oxide may also be an N-type semiconductor metal oxide or an inert metal oxide. The particle size is then between 2 and 10 nm.
    [0010] The thickness of this bonding layer may more particularly be adjusted, in view of the chemical nature of the particles, and in particular the nanoparticles, of metal oxide constituting it. In addition, the metal oxide particle sizes given above also correspond to the thickness of the dry layer formed with said particles. Thus, according to a first variant, the tie layer comprises at least one metal oxide chosen from the following metal oxides: V205, NiO, WO3, MoO3 and their mixtures, and has a thickness ranging from 2 nm to 200 nm. These metal oxides can also be used in hydrated form. According to a second variant, the tie layer comprises at least one metal oxide chosen from the following metal oxides: TiOx in which x is less than or equal to 2, ZnO and their mixtures, and has a thickness ranging from 2 nm to 10 nm . According to a third variant, the adhesive layer comprises at least one metal oxide chosen from the following metal oxides: Al 2 O 3, SiO 2 and their mixtures. In this case, the layer has a thickness ranging from 2 nm to 10 nm. This attachment layer of metal oxide (s) may advantageously be formed on the surface of the active electrical layer from a liquid mixture comprising the particles, in particular the nanoparticles, of metal oxides. As detailed below, these metal oxides can be deposited as such, but can also be generated in contact with the so-called active layer, from a precursor material undergoing, for example, a sol-gel type reaction.
    [0011] Thus, a solution of Zn (OAc) 2, 2H 2 O can be used as a precursor of ZnO oxide, just as a solution of vanadyl-triisopropoxide (VTIP) in isopropanol can be used as a precursor to oxide of V205. The conversion of the metal oxide precursor to the metal oxide is generally carried out by low temperature hydrolysis in the presence of the appropriate solvent (s). The adaptation of the experimental conditions is within the competence of those skilled in the art. Preferably, the particles, in particular the nanoparticles, of metal oxide are used in the form of a dispersion in a solvent, in particular an alcoholic solvent, generally without surfactant. Preferably, said alcoholic solvent is a primary alcohol, preferably a C2-C4 monoalcohol and in particular ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, or methylpropanol and mixtures of these solvents.
    [0012] In addition to the primary alcohol, the dispersion may also comprise a diol, in particular ethane-diol or propanediol. This liquid mixture containing the particles, and in particular the nanoparticles, of metal oxide (s) or the precursor material of metal oxide (s), can be deposited by any type of process by solvent or known wet way. More particularly, this process can be chosen from a strip casting process, for example by scraping ("doctor" blading in English language), by spin coating ("spin coating" in English), by "slot die coating", by jet of ink, by gravure, by screen printing.
    [0013] The oxide particles (s) metal (s) can also be deposited by evaporation. The deposition of this liquid mixture is advantageously carried out at a temperature below 100 ° C. and for example between room temperature and 100 ° C. The tie layer is then formed by exposing the assembly to various post-treatments such as annealing, especially at a temperature between 80 ° C and 130 ° C and for example for a period ranging from 5 minutes to 30 minutes . It is within the competence of those skilled in the art to implement a particular after-treatment adapted in particular to the type of metal oxide used, to the desired thickness for the tie layer.
    [0014] Generally, when a precursor of metal oxide (s) is considered to prepare the bonding layer based on metal oxide (s), it is preferable to carry out a subsequent annealing step. Electrically Active Layer The electrically active layer of organic electronic devices generally consists of a mixture containing at least two semiconductor materials: an electron acceptor type N material, and an electron donor type P material. The P-type semiconductor material contained in the active layer may be chosen from polymers containing thiophene units, polymers containing thienothiophene units, polymers containing diketopyrrolopyrrole units, polymers containing benzothiadiazole units, polymers containing units. thienopyrrolediones, polymers containing bithiophenedicarboximide units and polymers containing carbazole units. For example, the P-type semiconductor polymer is chosen from the following polymers: (poly (3-hexylthiophene) or P3HT, poly [N-9'-heptadecanyl-2,7-carbazole-alt-5,5 - (4,7-di-2-thienyl) -2 ', 1', 3'-benzothiadiazole or PCDTBT, poly [2,1,3-benzothiadiazole-4,7-diyl [4,4-bis-2- ethylhexyl) -4H-cyclopenta [2,1-b: 3,4-b] dithiophene-2,6-diyl]] or PCPDTBT, PBDTTPD, poly [[4,8-bis [(2-ethylhexyl) oxy benzo [1,2- b: 4,5 -13] dithiophene-2,6-diyl] [3-fluoro-2 - [(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl]] or PTB7.
    [0015] The P-type semiconductor material contained in the active layer may be chosen from P-type semiconductor molecules such as: porphyrin; 7,7 '- (4,4-bis (2-ethylhexyl) -4H-silolo [3,2-b: 4,5-b 2] dithiophene-2,6-diyl) bis (6-fluoro) 4- (5'-hexyl- [2,2'-bithiophen] -5-yl) benzo [c] [1,2,5] thiadiazole): DTS (FBTTh 2) 2; boron dipyromethines (BODIPY); molecules with triphenylamine nucleus (TPA). The N type semiconducting carbon material contained in the active layer is advantageously chosen from the materials containing patterns: 20-perylene-fullerenes, for example fullerene C60, fullerene C70, fullerene C80 or fullerene C84. - the semiconducting carbon nanotubes; graphene and nanographenes; And their soluble derivatives, such as methyl [6,6] -phenyl-C61-butyrate also known as PCBM or PC6iBM, methyl [6,6] -phenyl-C71-butyrate or PC71BM, a thiophene-C61-methyl butyrate, a multi-adduct of a C60 or C70 fullerene or functionalized carbon nanotubes; - N type polymers. Preferably, the N-type semiconductor material is chosen from materials containing fullerene units, in particular C 60, C 70, C 80 and C 84, the materials containing perylene units, in particular the following materials PC60BM. and PC70BM.
    [0016] The active layer is formed by different methods of depositing a liquid mixture comprising the P-type and N-type semiconductor materials, such as a spin-coating process. ), coating or a printing method such as inkjet, screen printing, slot-die coating, flexography, heliography. The active layer can also be formed by evaporation. In addition, a thermal treatment or annealing step may also be carried out at a temperature ranging from 50 ° C to 180 ° C for a time ranging from 1 to 30 minutes.
    [0017] P-type layer As mentioned previously, the present invention aims to improve the adhesion between the active layer and the P-type layer. The P-type layer is a P-type semiconductor layer called a "hole-transport layer". . According to the present invention, the P layer is a layer of poly (3,4-ethylenedioxythiophene): poly (styrene-sulfonate) (PEDOT: PSS). The PEDOT: PSS is used in a conventional solvent such as water, alcohols in particular primary alcohols, diols in particular ethane-diol and propanediol, glycol ethers and their mixture (s). ). This layer is dried at a low temperature, generally between room temperature and 140 ° C. The deposition of this layer is a knowledge of those skilled in the art. It is within the skill of those skilled in the art to choose the nature of the P layer and the electrodes according to the desired results.
    [0018] Electrodes Electrodes are usually made of metal or metal oxides or carbon. More particularly, in a reverse structure device, the cathode is a transparent conductive metal oxide and the anode is a metal.
    [0019] As a metal, there may be mentioned silver, copper, titanium, aluminum. As metal oxides (TCO), mention may be made of the compounds ITO (indium tin oxide), AZO (zinc oxide-aluminum), IZO (zinc oxide-indium) or FTO (doped tin oxide) F). We can also mention TCO / Metal / TCO multilayer stacks. In the devices according to the invention, the cathode is for example formed of an electrically conductive oxide and the anode is silver.
    [0020] N-type layer In the context of the present invention, the N-type layer comprises at least one metal oxide selected from TiOx in which x is less than or equal to 2, ZnO and mixtures thereof.
    [0021] The preparation and deposition of this layer are carried out in the same way as for the N-type tie layer. The organic electronic device according to the invention may be an organic photovoltaic (or solar) cell (PIN), a light-emitting diode organic or an organic photodetector, furthermore it may also be an organic electronic device of the "tandem" type. According to a first variant, the organic "tandem" electronic device according to the invention comprises first and second electrodes and an assembly comprising a multilayer stack containing a tie layer as defined according to the invention disposed between said electrodes.
    [0022] According to another variant, the "tandem" organic electronic device according to the invention comprises first and second electrodes and two sets each comprising a multilayer stack containing a tie layer as defined according to the invention disposed between said electrodes. By way of example, mention may be made of the devices according to the invention formed of the following layers deposited on the substrate such as PET and in which the upper electrode is preferably made of metal: TCO / N-layer / active layer / hook-layer / P layer / N layer / active layer / P layer / electrode; TCO / N layer / active layer / P layer / N layer / active layer / tie layer / P layer / electrode; TCO / N layer / active layer / hook layer / P layer / N layer / active layer / hook layer / P layer / electrode.
    [0023] These devices are represented respectively in FIGS. 3 to 5. EXAMPLES Example 1: Preparation of a stack for an OPV device incorporating a tie layer according to the invention Two types of tie layer are considered, one based on tungsten oxide (P-type oxide), and the other based on TiOx (N-type oxide). The WO 3 dispersion (2.5% by weight, without surfactant, 2-propanol base, particle size 10-20 nm crystalline structure: triclinic) is that of Nanograde Llc. The TiOx titanium oxide nanoparticle dispersion used is a dispersion in ethanol. The structure of the stack considered is as follows: Bonding layer Active layer N layer Conductive oxide Substrate The substrate is a PET substrate coated with a transparent conductive oxide with a square resistance of less than 15 Ohm sq-1. the layer N is a zinc oxide (ZnO); the active layer is a mixture of poly (3-hexylthiophene) and methyl [6,6] -phenyl-C61-butyrate (P3HT / PCBM); layer P is a layer of PEDOT: PSS of commercial formulation Clevios F010, Heraeus. The N and active layers as well as the tie layer are formed by spin-coating on a coated PET substrate. The thickness of the bonding layers formed is as follows: WO 3 - 50 nm; and 25 - TiOx - 10 nm.
    [0024] Example 2 Characterization of the Stacking Qualities of Example 1 a) Affinity Test The affinity of the tie layer for a representative formulation of a P type layer is assessed by a wettability test.
    [0025] The formulation P used is a layer of PEDOT: PSS of commercial formulation F010. Drop angle measurements are made under ambient conditions of temperature (-25 ° C) and humidity (-35%). The influence of each of the two bonding layers on the drop angle of a reference formulation P is detailed in Table 1 below: Table 1 Bond layer Drop angle - 40 ° W03 <100 TiOx 25 ° It is noted that the layer P has a good affinity for the tie layer (TiOx or WO3). Indeed, there is a decrease in the drop angle at the surface of the attachment layer compared to the active layer alone. b) Influence of the adhesion layer on the adhesion of the P layer The samples are prepared according to the standard protocol for producing OPV devices at CEA INES (Perrier et al., Solar Energy Materials and Solar Cells Volume 101, June 2012, Pages 210-216 The adhesion tests are carried out using a "Post-it" adhesive: The adhesive is placed by hand on the surface of the sample and removed manually. It has been appreciated with regard to a layer P formed in contact with the tie layer of the stacks prepared in Example 1. This layer P is a layer of PEDOT: PSS of commercial formulation Clevios F 010, Heraeus.
    [0026] The presence of the bonding layer makes it possible to improve the adhesion of the layer P. In fact, it is noted that without a bonding layer, the adhesion of the layer P to the active layer is very low. In the presence of an adhesion layer (TiOx or WO3), the P layer is not affected by the adhesion test and remains almost intact after the adhesion test. c) Evaluation of the performance of devices incorporating a stack according to those of Example 1 The OPV devices considered precede a multilayer stack as follows: Silver Layer P Layer Acid layer N layer Conductive oxide PET substrate The N layer is a layer Zinc oxide (ZnO) and the active layer is based on poly (3-hexylthiophene) and methyl [6,6] -phenyl-C61-butyrate (P3HT / PCBM). The P layer is a PEDOT: PSS layer (commercial formulation Clevios F 010, Heraeus). The different layers are formed by spin coating with the exception of the silver electrode.
    [0027] The active surface of the devices is 1.6 cm 2 and their performance was measured at 25 ° C under standard lighting conditions (1000 W / m2, AM 1.5G) (Table 2 below). The test parameters are: Voc: open circuit voltage; Jsc: short circuit current density; FF: "Fill factor" in English language: filling factor; PCE: "Power Conversion Efficiency" in English: power conversion efficiency. The test protocols are explained in the document Perrier et al. Solar Energy Materials and Solar Cells, Volume 101, June 2012, Pages 210-216.
    [0028] Table 2: Influence of the bonding layer on the performances of the devices Voc layer (mV) Jsc (mA cm-2) FF (%) PCE (%) of grip - 560.5 7.7 41.8 1, 80 WO3 561.3 8.0 38.7 1.75 TiOx 559.8 7.0 41.5 1.6 The performance of devices incorporating a tie layer is quite close to the reference value, particularly with the use of of W03.5
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. An organic electronic device containing first and second electrodes and at least one assembly comprising a multilayer stack disposed between said electrodes, said multilayer stack comprising successively: an N-type layer, an electrically-active layer, and a P-type layer base of a mixture of poly (3,4-ethylenedioxythiophene): poly (styrene-sulfonate), characterized in that said stack contains an additional layer called "tie layer" composed of at least one metal oxide and which is interposed between and in contact with the active layer and the P-type layer.
    [0002]
    2. Device according to claim 1, characterized in that the bonding layer is a layer of oxide (s) metal (s) in the form of nanoparticles.
    [0003]
    3. Device according to one of the preceding claims, characterized in that the adhesion layer is a layer comprising at least one metal oxide selected from the following metal oxides: V205, NiO, Mo03, WO3 and their mixtures and has a thickness ranging from 2 nm to 200 nm.
    [0004]
    4. Device according to one of claims 1 or 2, characterized in that the adhesive layer comprises at least one metal oxide selected from the following metal oxides: TiOx wherein x is less than or equal to 2, ZnO and their mixtures, and has a thickness ranging from 2 nm to 10 nm.
    [0005]
    5. Device according to one of claims 1 or 2, characterized in that the adhesive layer comprises at least one metal oxide selected from the following metal oxides A1203, SiO2 and mixtures thereof and has a thickness ranging from 2 nm to 25 nm. 10 nm.
    [0006]
    6. An organic electronic device according to one of the preceding claims, characterized in that the active layer is an N-type semiconductor material mixed with a P type semiconductor material.
    [0007]
    7. An organic electronic device according to the preceding claim, characterized in that the P-type semiconductor material is chosen from polymers containing thiophene units, polymers containing thienothiophene units, polymers containing diketopyrrolopyrroles units, polymers containing benzothiadiazole units. polymers containing thienopyrrolediones units, polymers containing bithiophenedicarboximide units and polymers containing carbazole units, and P-type semiconductor molecules selected from porphyrin; the: 7,7 '- (4,4-bis (2-ethylhexyl) -4H-silolo [3,2-b: 4,5-b 2] dithiophene-2,6-diyl) bis (6-fluoro) 4- (5'-hexyl [2,2'-bithiophen] -5-yl) benzo [c] [1,2,5] thiadiazole); bores-dipyromethene and triphenylamine ring molecules.
    [0008]
    8. An organic electronic device according to claim 6 or 7, characterized in that the N-type semiconductor material is chosen from materials containing fullerene units, in particular C 60, C 70, C 80 and C 84, the materials containing perylene units, in particular the following materials PC60BM and PC70BM.
    [0009]
    9. An organic electronic device according to one of the preceding claims, characterized in that the N-type layer comprises at least one metal oxide selected from the following metal oxides: TiOx in which x is less than or equal to 2, ZnO and their mixtures and has a thickness of between 2 nm and 200 nm. 15
    [0010]
    10. An organic electronic device according to one of claims 1 to 9, characterized in that it comprises first and second electrodes and an assembly comprising a multilayer stack containing a tie layer disposed between said electrodes.
    [0011]
    11. An organic electronic device according to one of claims 1 to 9, characterized in that it comprises first and second electrodes and two sets each comprising a multilayer stack containing a tie layer disposed between said electrodes.
    [0012]
    12. A method for preparing a multilayer stack comprising an electrically active layer superimposed on an N-type layer, characterized in that said method comprises the formation of a so-called "tie layer" sandwiched between and in contact with the so-called active layer and the P layer, said "tie layer" being formed of at least one metal oxide, preferably in the state of nanoparticles.
    [0013]
    13. Process for the preparation of an organic electronic device of inverse structure comprising at least the following steps: (i) having a substrate coated on one of its faces with a multilayer stack comprising in superposition order from said substrate: a conductive layer as a first electrode and an N-type layer; (ii) forming an electrically active layer on the N-type layer; (iii) contacting said active layer with a medium containing particles, and preferably nanoparticles, of at least one metal oxide, and exposing the assembly to conditions conducive to the formation of a so-called hook layer ; (iv) forming, by wet process, in contact with the tie layer, a P-type layer based on a mixture of two polymers, poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene) sodium sulphonate (PSS) said PEDOT: PSS; and (v) depositing in contact with the P-layer a conductive layer as a second electrode.
    [0014]
    A method for improving adhesion between an electrically active layer and a P-type layer in an organic electronic device, said method comprising forming a layer composed of at least one metal oxide at the intersection of the two layers.
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    Azarifar2013|Synthesis and characterization of organic conjugated polymer/ZnO nano-particle films for solar cell application
    同族专利:
    公开号 | 公开日
    US20160365526A1|2016-12-15|
    JP2017506815A|2017-03-09|
    EP3075015A1|2016-10-05|
    FR3013897B1|2017-05-12|
    WO2015079380A1|2015-06-04|
    KR20160090364A|2016-07-29|
    US9882155B2|2018-01-30|
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    法律状态:
    2015-11-30| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-30| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-29| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-29| PLFP| Fee payment|Year of fee payment: 7 |
    2020-11-30| PLFP| Fee payment|Year of fee payment: 8 |
    2021-11-30| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1361618A|FR3013897B1|2013-11-26|2013-11-26|ORGANIC ELECTRONIC DEVICES|FR1361618A| FR3013897B1|2013-11-26|2013-11-26|ORGANIC ELECTRONIC DEVICES|
    KR1020167016887A| KR20160090364A|2013-11-26|2014-11-25|Organic electronic devices|
    PCT/IB2014/066317| WO2015079380A1|2013-11-26|2014-11-25|Organic electronic devices|
    US15/039,486| US9882155B2|2013-11-26|2014-11-25|Organic electronic devices|
    JP2016534162A| JP2017506815A|2013-11-26|2014-11-25|Organic electronic devices|
    EP14812652.7A| EP3075015A1|2013-11-26|2014-11-25|Organic electronic devices|
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